Flame retardant epoxy molding compound, method and encapsulated device

ABSTRACT

An improved flame retardant epoxy molding compound comprises an epoxy, a hardener preferably of the novolac or anhydride type, a catalyst, a mold release agent, preferably a filler, preferably a colorant, preferably a coupling agent, an organic compound containing a higher percent of halogen (which can be part of the resin or the hardener), preferably the polyglycidyl ether of the bromophenol-formaldehyde novolac type, preferably containing at least about 1.0% of bromine by weight of the molding compound, a lower percent of sodium, preferably in the range of 0.03-0.06% by weight of the antimony pentoxide, a lower percent of antimony pentoxide, preferably in the range of ≦ about 0.8% by weight of the molding compound, and an amount of bismuth trioxide ≦ about 4.0% by weight of the molding compound. 
     The improved flame retardant epoxy molding compounds when used to encapsulated semiconductor devices have improved high temperature stability and compatibility, ball-lift performance, live-device performance, cost and lower toxicity compared to similar prior art molding compounds.

CROSS REFERENCES TO RELATED APPLICATIONS

This application is a divisional application of Ser. No. 07/418,757filed Oct. 5, 1989, U.S. Pat. No. 5,041,254 which in turn is acontinuation-in-part of application Ser. No. 07/258,574 filed Oct. 17,1988, now abandoned.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to an improved method of encapsulating asemiconductor device by heat curing an encapsulating compound comprisingan epoxy, a hardener, a catalyst, a mold release agent, optionally afiller, optionally a colorant, optionally a coupling agent and a flameretardant system around a semiconductor device.

In the improvement, the flame retardant system comprises a lowerpercentage of antimony pentoxide, a lower percentage of sodium and anorganic compound containing a higher percentage of halogen than priorart molding compounds.

In the improvement, molding compounds with an organic compoundcontaining a higher percentage of halogen along with a lower percentageof antimony pentoxide and sodium have the unexpected results ofreleasing less free bromine ion upon heat aging and water extractionthan prior art molding compounds. Also when the improved moldingcompounds were molded onto a semiconductor device, they exhibitunexpected superior high temperature stability and compatability, balllift and live device performance.

The present invention also relates to improved flame retardantthermosetting epoxy molding compounds of the type comprising an epoxy, ahardener, a catalyst, a mold release agent, optionally a filler,optionally a colorant, optionally a coupling agent and a flame retardantsystem wherein the flame retardant system comprises a lower percentageof antimony pentoxide, a lower percentage of sodium, an organic compoundcontaining a higher percentage of halogen than prior art moldingcompounds and optionally a basic metal oxide to reduce corrosion ofmetal conductor lines and pads of the semiconductor device.

The present invention also includes an improved encapsulatedsemiconductor device wherein the encapsulant is as described above, withas flame-retardant system comprising a lower percentage of antimonypentoxide, and sodium, an organic compound containing a higherpercentage of halogen than prior art molding compounds and optionally abasic metal oxide to reduce corrosion of metal conductor lines and padsof the semiconductor device.

In all three instances the halogen-containing organic compound may be aseparate ingredient, but is preferably a part of either the epoxy or thehardener. The halogen containing organic compounds can also behalogen-containing compounds which become chemically incorporated intothe product of the epoxy resin and the hardener upon setting or part ofother ingredients such as the lubricant or the colorant.

The term "epoxy molding compounds" as used herein means epoxy moldingcompound conventionally known in the art including any materialcontaining two or more reactive oxirane groups. For example, the epoxymolding compound may have two or more epoxy groups in one molecule,including glycidyl ether type such as bisphenol A type, phenol novolactype, cresol novolac type and the like; glycidyl-ester type; alicyclictype; heterocyclic type and halogenated epoxy resins etc. The epoxyresins may be used either singly or as a mixture of two or more resins.

Similarly, the term "epoxy novolac molding compound" as used hereinincludes any phenol-derived and substituted phenol derived novolachardener conventionally used as hardener for epoxy resins. For example,phenolic novolacs, cresolic novolacs and Bisphenol A derivatives aresuitable. The epoxy novolac molding compounds may be used either singlyor as a mixture of two or more compounds.

The term "catalyst" as used herein means a catalyst appropriate to thehardener used to promote the curing of the present composition. Suchcatalysts include basic and acidic catalysts such as the metal halideLewis acids, e.g., boron trifluoride, stannic chloride, zinc chlorideand the like, metal carboxylate-salts such as stannous octoate and thelike; and amines, e.g., triethylamine, imidazole derivatives and thelike. The catalysts are used in conventional amounts such as from about0.1 to 5.0% by weight of the combined weight of epoxy and hardener.

The term "mold release agents" as used herein means chemical agentscommonly used to assist the release of the cured epoxy molding compoundsfrom the mold. For example, carnauba wax; montanic acid ester wax;polyethylene wax; polytetrafluoroethylene wax; glyceral monostearate;metallic stearates; paraffin waxes and the like are suitable.

The term "fillers" as used herein means one or more of the conventionalfillers such as silica, calcium carbonate, calcium silicate, aluminumoxide, glass fibers, clay, and the like. The preferred filler is silicaor a mixture of predominantly silica with other filler(s). The fillersusually are used in at least 50 percent by weight of the moldingcompound.

The term "colorant" as used herein includes colorant commonly used inepoxy molding compound, such as carbon black, pigments, dyes and thelike.

The term "coupling agent," as used herein means a coupling agent knownto improve wet electrical properties of the compound. The couplingagents may be of the silane type, characterized by the formula R'Si(OR)₃; where R' represents an organo-functional group such as amino,mercapto, vinyl, epoxy or methacryloxy, and OR represents a hydrolyzablealkoxy group attached to the silicon. Preferred coupling agents aredescribed in U.S. Pat. Nos. 4,042,550 and 3,849,187, of which thedescriptions are incorporated herein by reference.

The term "halogen-containing organic compound" or "organic compoundcontaining halogen", as used herein, includes organic compound in whichthe halogen is present from any source including halogenation of acomponent or its precursor (such as a monomer) or by addition ofhalogen-containing monomers by reactions in which the halogen is notcompletely removed.

The halogen-containing organic compound used in a flame retardant systemis preferably of the reactive type and further preferably has, ashalogen, chlorine or bromine. Exemplary halogenated organic compoundsare those types of polyglycidyl ether of bromophenol-formaldehydenovolac, commercially sold by Nippon Kayaku under the tradename "Bren™"and is of the general formula I: ##STR1## Other exemplary halogenatedorganic compounds are described in U.S. Pat. Nos. 4,042,550 and4,282,136, of which the descriptions are incorporated herein byreference and include halogenated bisphenol A and derivatives ofbisphenol A such as tetrabromobisphenol A. Additional examples ofreactive halogenated organic compounds which are a part of the epoxyresins are glycidyl ethers of halogenated resins such as the diglycidylether of tetrabromobisphenol A.

The halogen containing organic compound may be a separate additive ormay be contained in one or more of the organic components of the moldingcompound, especially the epoxy or the hardener, or possibly othercomponents such as the lubricant, or the colorant or the filler (iforganic).

Exemplary of reactive halogen-containing organic compounds which arepart of the hardener are halogenated anhydrides such as tetrabromo andtetrachloro-phthalic anhydride. Tetrabromobisphenol A and other suchhalogenated monomers may also be considered part of the hardener,especially the phenol-derived or substituted phenol-derived hardener.

The term "antimony pentoxide" as used herein means antimony pentoxide inany available form. Preferably, antimony pentoxide used is Nyacol A1590commercially sold by the Nyacol Division of P.Q. Corporation which has avery low sodium content of 0.03 to 0.06% by weight of the antimonypentoxide as compared to that of 3 to 4% in prior art products such asNyacol A1588LP.

The term "basic metal oxide" as used herein means any metal oxide in anyavailable form capable of neutralizing the acidity of the antimonypentoxide and thereby reducing the corrosion of the metal semiconductordevice lines and pads, especially in regions where two different metalsare in contact with each other. Preferably, the basic metal oxide isbismuth trioxide (Bi₂ O₃).

2. Description of Background Art

Epoxy resin compounds have often been used for encapsulation ofsemiconductor or device such as integrated circuits (IC), large scaleintegrated circuits (LSI), transistors and diodes, etc., or otherelectronic components. Such encapsulants generally comprise an epoxy, ahardener, a catalyst, a mold release agent, optionally a filler,optionally a colorant and sometimes a coupling agent.

Exemplary formulations of these ingredients are described in U.S. Pat.Nos. 4,710,796 to Ikeya et al., 4,282,135 to Hunt et al., U.S. Pat. No.4,042,550 and references cited therein. Recently, the electronicindustries require these epoxy molding compounds be flame retardant.Additives including halogenated compounds, transition metal oxides andhydrated alumina to improve the flame retardancy, as measured forexample by Underwriters Laboratory Test 94V-0 of 1/16" bar have beenreported. However, at high temperatures, these flame retardant additivesdetract from the compatibility of the encapsulant with semiconductordevices.

U.S. Pat. No. 4,710,796 to Ikeya et al. teaches a resin forencapsulating semiconductor device comprising an epoxy resin, curingagent, organic phosphine compound and at least one antimony oxide.

U.S. Pat. No. 4,042,550 teaches epoxyanhydride molding compounds withsecondary fillers including antimony trioxide or antimony tetraoxide andhalogenated compounds in flame retardant systems.

Similarly, U.S. Pat. No. 4,282,136 to Hunt et al. describes the use ofsynergistic flame retardants consisting of halogen-containing organiccompounds and antimony pentoxide. The reference teaches that anencapsulant employing such a flame retardant system, when used toencapsulate a semiconductor device, has improved high temperaturecompatibility compared to similar molding compounds with antimonytrioxide or antimony tetraoxide. However, the prior art epoxy moldingcompounds contains a high percent of sodium which is known to cause poorperformance in semiconductor devices due to current leakage. See Moltzanet al., The Evolution of Epoxy Encapsulation Compounds For IntegratedCircuits: A User's Perspective, Polymer for High Technology Electronicsand Protronics, ACS Sym. Series No. 346, p. 521, Sep. 7-12, 1986.

While the prior art flame retardant combinations provides reasonableflame retardance and satisfactory compatibility on electronic devices, aneed clearly exists for flame retardant epoxy molding compounds of alltypes with improved compatibility, performance, cost and lower toxicity.

Accordingly, it is an object of the present invention to provide animproved flame retardant thermosetting epoxy molding compound.

It is yet another object of the present invention to provide an improvedmethod of encapsulating a semiconductor device.

It is yet another object of the present invention to provide an improvedencapsulated semiconductor device.

These and other objects of the invention, as well as a fullerunderstanding of the advantage thereof, can be had by reference to thefollowing descriptions and claims.

SUMMARY OF THE INVENTION

The foregoing objects are achieved according to the present invention byan improved epoxy molding compound comprising:

(a) about 5-25 percent by weight of compound of an epoxy;

(b) about 4-20 percent by weight of compound of a phenol-derived or asubstituted phenol derived resin hardener;

(c) an effective amount of a catalyst for the reaction between saidepoxy resin and said hardener in an amount of from about 0.1 to 10% byweight of the combined weight of epoxy and hardener;

(d) an effective amount of a mold release agent for the release of thecured molding compound from a mold in an amount of between about 0.01and about 2 percent by weight of composition;

(e) between about 50 and 85 percent by weight of composition of afiller; and

(f) a flame retardant system of:

(1) ≦about 0.8% antimony pentoxide by weight of molding compound;

(2) from about 0.01-1% sodium by weight of antimony pentoxide; and

(3) a reactive organic compound containing at least about 1.0% ofbromine by weight of molding compound which may include one or more ofthe other components; and

(4) ≦about 4.0% by weight of molding compound of a basic metal oxidewhich is most preferably bismuth trioxide.

Accordingly, Table 1 below summarizes the improved epoxy moldingcompounds.

                  TABLE 1                                                         ______________________________________                                                                     Preferred                                        Description         Range    Range                                            Formulation A:      (%)      (%)                                              ______________________________________                                        Epoxy Cresol Novolac resin                                                                         5-25    10-16                                            epoxy resin (preferably                                                                           at least 1.0-1.8                                          BREN ™) -containing                                                                            about 1.0                                                 bromine (%)                                                                   sodium (present in the                                                                            0.01-1   0.03-0.06                                        antimony pentoxide)                                                           antimony pentoxide  ≦0.80                                                                           0.40-0.80                                        bismuth trioxide    ≦4.0                                                                            1.60-3.20                                        Carbon black colorant                                                                             0.05-0.5 0.1-0.5                                          phenol Novolac Hardener                                                                            4-20     4-12                                            Fused Silica (SiO.sub.2) filler                                                                   50-85    60-80                                            silanes             0.05-2.0 0.1-1.5                                          catalysts           0.01-10.0                                                                              0.5-2.0                                          wax lubricants      0.01-2   0.02-1.0                                         ______________________________________                                    

The improved epoxy molding compounds of the present invention aresuitable for use in encapsulating a semiconductor device.

According to the present invention, the said improved epoxy moldingcompounds may be prepared by any conventional method. For example, theingredients may be finely ground, dry blended and then densified on ahot differential roll mill, followed by granulation. Generally, theingredients (or any portion of them) may be prepared as a fine powder,fed directly into a compounding device such as an extruder prepared as apremix of raw materials. If less than all of the ingredients are presentin the initial form, the remainder of the ingredients can be added priorto or during densification.

Densification can be by mechanical compacting using a preformer or acombining mill in the case of a fine powder, or by an extruder ordifferential roll mill in the case of the fine powders, direct feed orpremix. Premixes or densified forms (such as preforms and granularforms), containing less than all of the ingredients can also be fed tothe ultimate mold in the system with the remaining ingredients in asimilar or different form.

The present invention includes flame retardant molding compounds in anyphysical form or even as systems of two or more components. Where two ormore components are used, one should contain the epoxy, the other thehardener. Preferably, the catalyst is in the hardener component to avoidcatalyzed homopolymerization of the epoxy.

In a preferred embodiment, in the laboratory, the dry ingredients of theformula are preground to a fine powder and then mixed in a large plasticbag. The liquid ingredients (i.e., the silane coupling agents) are addedto dry ingredients and the mixture is mixed again by hand. The mixtureis then treated on a large two-roll mill (one roll heated to ˜90° C. andthe other cooled with tap water) until a uniform sheet (˜6" wide by 24"long) is obtained. The sheet is allowed to cool and then ground to afine powder.

In another preferred embodiment, in the pilot plant and during largescale production, the dry ingredients are mixed in a large hopper, theliquid ingredients are added in a homogeneous manner to ensure blending,and mixing continues. This mixture is then extruded (with heating) togive a continuous sheet which is cooled and grounded. The final groundpowder can be used as is, or compacted (densified) in a preformer togive tablets (performs) of desired shape and size.

These compounds may be molded into various articles by application ofthe appropriate temperature and pressure. For example, moldingconditions for the encapsulated semiconductor of the present inventionmay range from about 300° to 400° F., (about 149°-204° C.), preferablyabout 350° to about 375° F., (about 177°-191° C.), at 400 to 1,500 psi,(about 28-105 kg/cm²), for a time ranging from about 30 to 120 seconds,preferably 60 to 90 seconds.

Any suitable molding apparatus may be employed, such as a transfer pressequipped with a multi-cavity mold.

The ratio between the various ingredients may vary widely. In general,the epoxy will be in proportion to a novolac hardener so as to give amole ratio of oxirane:reactive hydroxy between about 0.8 and 1.25.Similarly, the epoxy will be in proportion to an anhydride hardener soas to give a ratio of oxirane:anhydride equivalent between about 1.0 and1.7, preferably between about 1.11 and 1.25.

The catalyst employed is generally applied at levels sufficient toharden the epoxy molding compound under anticipated molding conditions.Amounts between about 0.1 and 5 weight percent (by combined weight ofepoxy and hardener) are sufficient.

The mold release agent will be employed in amounts sufficient to givegood release from the mold and also to improve the wet electricalproperties of the encapsulated semiconductor device. Amounts betweenabout 0.01 and 2 percent by weight of total compound, preferably betweenabout 0.02 and 1 percent by weight of total compound can be used.

The total amount of filler may range from 0 up to about 85 percent ofthe total compound. Preferably, the filler comprises a total of morethan 50 weight percent of the total compound and more preferably betweenabout 60 and about 85 weight percent of the total compound. Also,preferably, between about 60 and about 80 weight percent of the totalcompound is a silica filler.

Colorants, if employed, are generally in amounts sufficient to giveencapsulated devices the desired color preferably black. Amounts betweenabout 0.1-1.5% by weight of total compound can be employed.

Coupling agents, and in particular silane coupling agents, are providedin amounts sufficient to give the desired wet electrical properties andpreferably between about 0.05 and 2 weight percent by total weight ofcompound, more preferably between about 0.1 and 1.5 weight percent bytotal weight of compound.

The epoxy molding compound obtained may be used to encapsulatesemiconductor devices by any conventional method. For example, thepreferred improved epoxy molding formulations comprising 0.4-0.8%percentage of antimony pentoxide; 0.03-0.06% sodium content (by weightof antimony pentoxide) and an organic compound containing about 1.0-1.8%of bromine when molded on test devices have unexpected superior thermaldevice compatibility, flameretardancy, ball lift property, live deviceperformance compared to prior art formulations as disclosed in U.S. Pat.No. 4,282,136 to Hunt et al.

The use of a lower percentage of antimony pentoxide in the presentinvention is preferred because antimony pentoxide is expensive andtoxic.

Improved epoxy molding formulations comprising 0.4-0.8 percent ofantimony peroxide, 0.03-0.06 percent of sodium (by weight of antimonypentoxide) and an organic compound containing about 1.0-1.8 percent ofbromine; when molded on test devices (autoclave) give superior ball lifttest results. The ball lift (autoclave) test is routinely performed bysemiconductor manufacturers to assess reliability of the devices in ahumid environment. In the ball lift test, percent of ball bonds liftedwhen pulled and loss of bond strength as a function of the number ofhours the devices held in an autoclave under two conditions (121° C., 15psi steam and 135° C., 30 psi steam) are measured.

The improved epoxy molding formulations are uniquely effective indelaying or eliminating the "ball lift problem" in a moldedsemiconductor device. The improved epoxy molding compound shows no balllift out to 1200 hours at both 15 and 30 psi while comparable samplewith antimony trioxide shows 50% ball lift in 370 hours at 30 psi.

Further the improved epoxy molding compounds unexpectedly give superiorlive-device performance than the other combination of brominated resinand antimony trioxide/pentoxide. In the live-device performance test,National Semiconductor LF412 operational amplifiers are encapsulatedwith the improved epoxy molding compound. A group of about 40 of thesemolded packages (14 pin dual in-line) are subject to a high humidityenvironment (131° C., 100% relative humidity in an autoclave at 30 psigauge pressure) with no bias. The parts are then pulled from theautoclave at regular intervals and examined for electrical failure (gainless than 7 or greater than 65).

Nineteen of the thirty eight National Semiconductor LF412 operationalamplifiers encapsulated with the improved epoxy molding compound remainoperational after 3036 hours of testing. On the other hand, nineteen ofthe thirty-eight operational amplifiers molded with comparable prior artcompound containing 2.4 percent antimony pentoxide failed in less than198 hours.

This is especially surprising in view of the prior art teaching that ahigher percent antimony pentoxide (≧1%) will give formulation withbetter synergistic performance. One skilled in the art of moldingcompound systems would not be lead to use ≦ about 0.8% antimonypentoxide because prior art teaches ≦ about 0.8% antimony pentoxide isexpected to give poor flame retardancy and also insufficient to giveimproved "ball lift" performance.

It is well known in the art that the interaction of organic brominatedspecies with the Au/Al intermetallic is the predominant failuremechanism, causing "ball lift" problems. (See Khan et al., Effect ofHigh Thermal Stability Mold Material On the Gold-Aluminum BondReliability in Epoxy Encapsulated VLSI Devices, in Proc. IEEE. Paperpresented at the Int. Reliability Physics Symp., pp. 40-49, April,1988). Thus the use of an organic compound containing a higher amount ofbromine, as flame-retardants, in molding compound compositions to giveimproved ball-lift and live device performance is unexpected.

The use of an organic compound containing a higher percent of bromine inthe improved epoxy molding compound has the unusual properties ofreleasing less free bromine ion, upon heat aging and water extractionthan prior art compounds.

The free bromine ion released from the molding compounds is determinedby the "bromine extraction test." In the bromine extraction test, themolding compound is heat cured at 175° C. for 4 hours. The curedcompound is then grounded and screened through 35-mesh sieve. The sievedcompound is then heat aged at specific temperatures, preferably in therange from 200°-240° C. At specific intervals, small amounts of compoundare removed. A one gram sample is then mixed with 100 ml of deionizedwater and reflux for 24 hours. The amount of free bromine ion extractedfrom the compound is then determined by ion chromatography.

In the present invention, after exposing the molding compounds at 200°C. for 500 hours, bromine ion extracted by water was 175 ppm for thedevice with the improved epoxy molding compound and 400 ppm for theprior art molding compound devices. At 240° C., after 500 hours, bromineextracted by water was 240 ppm for improved epoxy molding compounddevices and 1000 ppm for prior art epoxy molding compound devices.

The present invention is not restricted to the above ingredients but mayinclude other ingredients which do not detract from flame retardantproperties of the flame retardant agent. Accordingly, other organic orinorganic materials may be added under the above conditions, includingantimony trioxide and antimony tetraoxide in total amounts less than theamount of antimony pentoxide. Additionally, basic metal oxides such asbismuth trioxide may be added to further improve the live deviceperformance of the encapsulated semiconductor devices.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 describes test results of the ball lift (autoclave) test onmolded devices (Examples 6-9) as a function of time and the estimatedhours of 50% occurrence of ball lift at 15 psi.

FIG. 2 describes test results of the ball lift (autoclave) test onmolded devices (Examples 6-9) as a function of time and the estimatedhours of 50% occurrence of ball lift at 30 psi.

FIG. 3 describes test results of the ball lift test on the encapsulateddevices Example 14.

FIG. 4 describes test results of the bromine extraction test performedat 200° C. upon the molding compound from Example 14.

FIG. 5 describes test results of the bromine extraction test performedat 240° C. upon the molding compound from Example 14.

FIG. 6 describes test results of the ball lift (autoclave) test on theencapsulated devices Examples 14 and 19-21 as a function of time at 15psi.

FIG. 7 describes test results of the ball lift (autoclave) test on theencapsulated devices Examples 14 and 19-21 as a function of time at 30psi.

DESCRIPTION OF PREFERRED EMBODIMENTS

The following nonlimiting examples further illustrate the presentinvention relating to an improved epoxy molding compound, method andencapsulated device. All parts are by weight unless indicated otherwise.

EXAMPLES 1-4

Epoxy encapsulants are prepared from the modified formulation Aindicated in Table 2. The four groups of formulation differ in thepresence/absence of antimony trioxide and/or brominated resin of thefollowing type. ##STR2##

                  TABLE 2                                                         ______________________________________                                                       Examples                                                       Description      1      2        3    4                                       molding compound %      %        %    %                                       ______________________________________                                        Crystalline silica                                                                             71.36  73.76    71.36                                                                              73.76                                   filler                                                                        Carbon black coloring                                                                          0.23   0.23     0.23 0.23                                    Phenol Novolac   8.64   8.64     9.06 9.06                                    Hardener                                                                      Epoxy Cresol Novolac                                                                           15.00  15.00    15.82                                                                              15.82                                   resin                                                                         Silane coupling agent                                                                          0.48   0.48     0.48 0.48                                    catalyst         0.25   0.25     0.25 0.25                                    wax lubricants   0.40   0.40     0.40 0.40                                    Brominated bis-A*                                                                              1.24   1.24     --   --                                      type resin                                                                    antimony trioxide                                                                              2.40   --       2.40 --                                      ______________________________________                                         *A tetrabromobisphenolA glycidyl ether resin with a softening point of        70-80° C. determined by Durran's method, an epoxy equivalent weigh     of 450-470, and 49 percent by weight of bromine.                         

EXAMPLE 5

The four compounds as described in Examples 1-4 are molded onto testdevices and then subjected to the ball lift (autoclave) test. The testresults as a function of time and the estimated hours to 50% occurrenceof ball lift, or hours to 50% of initial bond-pull strength aresummarized in Table 3.

                  TABLE 3                                                         ______________________________________                                        LS00 - Bond Strength and Ball Lift                                                    Hours to 50%      Hours to 50%                                                Pull Strength     Ball Lift                                           psi       15 psi   30 psi     15 psi 30                                       ______________________________________                                        Examples                                                                      1            540   230           460 160                                      2           1040   410           910 350                                      3            630   200           500 180                                      4         >>1300   1170       >>1300 1130                                     ______________________________________                                    

A review of the data shows that the gold wire ball bond to the aluminumbonding pad on the devices are degraded (loss of physical bondingstrength) by the presence of the flame-retardant ingredients (brominatedresin of the bis-A type and antimony trioxide) in the plasticencapsulant under the high moisture environment of the autoclave.Specifically, the presence of antimony trioxide is found to be theoverriding factor in causing ball lift, with the brominated resinplaying a secondary role and only when the antimony content is lowered.When both of these ingredients are absent [Example 4], ball lift couldnot be detected out to 1300 hours at 15 psi.

EXAMPLES 6-9

A series of epoxy encapsulant compounds comparing the effectiveness ofantimony pentoxide and trioxide as a flame retardant synergist areprepared in the laboratory then molded on test devices as indicated inTable 4.

                  TABLE 4                                                         ______________________________________                                        molding   Examples                                                            compound  6          7         8      9                                       ______________________________________                                        Brominated                                                                              Brominated*                                                                              Brominated                                                                              Bren ™                                                                            Bren ™                               Resin     Ether      Ether                                                    Bromine in                                                                               .60        .60       .895   .895                                   resin (%)                                                                     Antimony  2.4        --        0.80   --                                      Trioxide (%)                                                                  Antimony  --         2.4       --     0.80                                    Pentoxide (%)                                                                 ______________________________________                                         *The brominated resin is a tetrabromobisphenol-A glycidyl ether resin wit     a softening point of 70-80° C. determined by Durran's method, an       epoxy equivalent weight of 450-470, and 49 percent by weight of bromine. 

EXAMPLE 10

The properties of the cured encapsulants of Examples 6-9 are furtherdetermined by total burn times of 1/16" bar according to UL-94V-0. Thetest results are summarized in Table 5.

                  TABLE 5                                                         ______________________________________                                               1/16" Bars                                                                             Total                                                         Example #                                                                              1st Burn/2nd Burn/Burn Time                                                                      94V-0 Status                                      ______________________________________                                        6        0       6        19 sec  Pass                                                 0       2                                                                     2       0                                                                     0       6                                                                     1       2                                                            7        4       6        28      pass                                                 0       2                                                                     2       5                                                                     2       2                                                                     3       2                                                            8        2       5                                                                     1       5        54      Fail.sup.+                                           2       4                                                                     0       3                                                                     2       30                                                           9        2       30       88      Fail.sup.+                                           8       2                                                                     3       6                                                                     5       4                                                                     3       25                                                           ______________________________________                                         .sup.+ The encapsulated device failed the UL94V-0 test for 1/16"  bar         because only 0.89% of bromine (2.5% of Bren ™) is used in the molding      compound. The encapsulated device will pass the UL94V-0 test if 1/8" bar      or at least 1.0% of bromine is used in the molding compound.             

In contrast to prior art teachings, the data in Table 5 shows antimonypentoxide give poorer flame-retardance relative to antimony trioxide asmeasured by (UL-94V-0) total burn times of 1/16" bar.

EXAMPLE 11-12

The molded devices (Examples 6-9) are subjected to the ball lift(autoclave) test as described in Example 5. The test results as afunction of time and the estimated hours of 50% occurrence of ball liftat both 15 and 30 psi conditions are summarized in Table 6 and FIGS.1-2.

                  TABLE 6                                                         ______________________________________                                        LF412R - Bond Strength and Ball Lift                                                     Hours to    Hours to                                                          50% Pull Strength                                                                         50% Ball Lift                                          Example                                                                              Description                                                                             15 psi   30 psi 15 psi 30 psi                                ______________________________________                                        6                  1430      300   1430    280                                7                >>1500    ˜1100                                                                         >>1500  ˜1000                          8                 >1500      400  -1530    370                                9                >>1500   >>1200 >>1500 >>1200                                ______________________________________                                    

A review of the data shows that when antimony pentoxide is used in placeof antimony trioxide, the ball lift problem is either delayed or it cannot be detected at all, depending on the brominated resin used. The twosamples with antimony pentoxide (7 and 9) show much reduced ball liftcompared to samples 6 and 8. Also, sample 9 shows no ball lift out to1200 hours at both 15 and 30 psi, while the comparable sample (8) withantimony trioxide shows 50% ball lift in 370 hours at 30 psi.

EXAMPLE 13

National Semiconductor LF412 operational amplifiers are encapsulatedwith encapsulants described in Examples 6-9. A group of about 40 ofthese molded packages (14 pin dual in-line) are subjected to the livedevice performance test.

The results of the live device test are summarized in Table 7.

                  TABLE 7                                                         ______________________________________                                        Live Device Performance at 30 psi, no bias of LF412                           Operational Amplifiers in 14 pin DIP packages                                 encapsulated with molding compounds from Examples 6-9                         ______________________________________                                        Examples     6        7         8       9                                     Initial Number                                                                             37       38        40      38                                    of Sample Devices                                                             Hours        Cumulative Number of Failures                                    ______________________________________                                          0          0         0        0       0                                      44          0         0        0       0                                      154         0         8        0       0                                      198         l        22        0       2                                      286         2        23        1       2                                      352         2        26        1       2                                      440         3        28        2       3                                      506         3        32        2       3                                      594         4        No        2       3                                      660         5        Further   2       3                                      748         5        Testing   4       3                                      792         5                  4       3                                      924         18                 13      9                                     1056         19                 13      9                                     1210         22                 13      9                                     1364         28                 19      11                                    1518         No                 22      12                                    1672         Further            23      12                                    1826         Testing            28      12                                    1980                            No      15                                    2134                            Further 18                                    2442                            Testing 19                                    2750                                    19                                    3036                                    19                                    ______________________________________                                    

A review of the data shows that the combination of Bren™ and antimonypentoxide in the improved molding compound encapsulated device givessuperior live-device performance than the other combination ofbrominated resin and antimony trioxide/pentoxide.

EXAMPLE 14

On a pilot plant scale epoxy encapsulants are prepared from theformulation indicated in Table 8. The improved molding compound is thenmolded onto test devices as in Example 5.

                  TABLE 8                                                         ______________________________________                                                            Example                                                   Description         14                                                        ______________________________________                                        Epoxy Cresol Novolac resin                                                                        13.26                                                     epoxy resin (BREN ™) -                                                                         1.36.sup.+                                                containing bromine (%)                                                        antimony pentoxide  0.75.sup.++                                               Carbon black coloring                                                                             0.20                                                      Phenol Novolac Hardener                                                                           9.10                                                      Fused Silica (SiO.sub.2) filler                                                                   71.39                                                     Silane coupling agent                                                                             0.70                                                      catalysts           0.35                                                      wax lubricants      0.45                                                      ______________________________________                                         .sup.+ The 1.36% of bromine equivalents to 3.8% Bren                          .sup.++ The level of 0.75% commercial antimony pentoxide represents an        actual level of 0.67-0.68%                                               

EXAMPLE 15

The properties of cured encapsulants of Example 14 are tested accordingto UL-94V-0 (one sixteenth inch). The test results are summarized inTable 9.

                  TABLE 9                                                         ______________________________________                                               1st Burn    2nd Burn                                                   ______________________________________                                        Example  0             2        Pass                                          14*      0             0                                                               1             1                                                               0             0                                                               0             0                                                      ______________________________________                                         *Example 14 is molded at 350° F., postcured six hours at               175° C.                                                           

EXAMPLE 16

The encapsulated device from Example 14 is subjected to the ball lifttest. Test results are summarized in FIG. 3. The test results show thatthe cured encapsulant of Example 14 does not cause degradation of thewire bond strength after 1500 hours at 135° C., 30 psi steam.

EXAMPLE 17

The molding compound from Example 14 is subjected to the bromineextraction test. Test results are summarized at FIG. 4.

The test results show that the heat cured molding compound of Example 14after heat aging at 200° C. for 500 hours releases bromine ion extractedby water of 175 ppm concentration. This is far lower than the 400 ppmwater extractable bromine ion concentration released by encapsulant ofprior art epoxy molding compounds under the same condition.

EXAMPLE 18

The bromine extraction test as described in Example 17 was repeated forthe molding compound from Example 14 at 240° C. Test results aresummarized in FIG. 5. The test results show that the heat curedencapsulant molding compound of Example 14 after heat aging at 240° C.for 500 hours releases bromine ion extracted by water of 240 ppmconcentration. This is far lower than the 1000 ppm water extractablebromine ion concentration released by encapsulant of prior art epoxymolding compound under the same condition.

EXAMPLE 19-21

Epoxy encapsulants (Examples 19-21) using 0.75% Sb₂ O₃, 0.50% Sb₂ O₃/0.25% Sb₂ O₅ and 0.25% Sb₂ O₃ /0.50% Sb₂ O₅ respectively are preparedin the laboratory. Examples 19-21 are of similar compositions as used inExample 14 except that antimony trioxide or a mixture of antimonytrioxide/pentoxide are used in place of antimony pentoxide.

EXAMPLE 22

The epoxy molding compounds prepared in Examples 19-21 are molded ontest devices as in Example 14.

The encapsulated devices from Examples 14, 19-21 are subjected to theball lift test as described in Example 5. Test results as a function oftime at both 15 and 30 psi conditions are summarized in FIGS. 6 and 7respectively. The improved epoxy molding compound as described inExample 14 containing 0.75% antimony pentoxide gives superior ball liftperformance than the other combination of brominated resin and antimonytrioxide/pentoxide mixtures.

EXAMPLES 23-25

Epoxy encapsulants are prepared from the formulations indicated in Table10. The formulations are similar to that presented in Table 8 except forthe content of antimony pentoxide and bismuth trioxide.

                  TABLE 10                                                        ______________________________________                                                      Example                                                         Description     23         24      25                                         ______________________________________                                        Epoxy Cresol Novolac resin                                                                    13.26      13.26   13.26                                      epoxy resin (BREN ™) -                                                                     1.36.sup.+ 1.36.sup.+                                                                            1.36.sup.+                                 containing bromine (%)                                                        bismuth trixoide                                                                              --         1.6     1.6                                        antimony pentoxide                                                                            0.4        --      0.4                                        Carbon black coloring                                                                         0.20       0.20    0.20                                       Phenol Novolac Hardener                                                                       9.10       9.10    9.10                                       Fused Silica (SiO.sub.2) filler                                                               71.39      71.39   71.39                                      Silane coupling agent                                                                         0.70       0.70    0.70                                       catalysts       0.35       0.35    0.35                                       wax lubricants  0.45       0.45    0.45                                       ______________________________________                                         .sup.+ The 1.36% of bromine equivalents to 3.8% Bren                     

EXAMPLE 26

National Semiconductor LF412 operational amplifiers are encapsulatedwith encapsulants described in Examples 23-25. A group of about 40 ofthese molded packages (14 pin dual in-line) are subjected to the livedevice performance test at 15 psi and no bias of the operationalamplifiers.

The results of the live device test are summarized in Table 11.

                  TABLE 11                                                        ______________________________________                                        Live Device Performance at 15 psi, no bias of LF412                           Operational Amplifiers in 14 pin DIP packages                                 encapsulated with molding compounds from Examples 23-25                       ______________________________________                                        Examples  23           24        25                                           Initial # of                                                                            38           37        36                                           Sample Devices                                                                          Cumulative Number of                                                Hours     Parametric Failures                                                 ______________________________________                                         44       1            1         0                                             88       2            1         0                                             176      2            1         0                                             242      5            1         0                                             330      6            1         0                                             396      7            3         0                                             440      10           5         0                                             506      11           5         0                                             594      14           10        3                                             660      20           16        7                                             748      24           17        11                                            814      No further   28        17                                            924      testing      No further                                                                              17                                           1056                   testing   20                                                                            No further                                                                    testing                                      ______________________________________                                    

The test data indicates that the combination of antimony pentoxide andbismuth trioxide at the same level of Bren™ (Example 25) gives superiorlive-device performance than the formulation having antimony pentoxidealone or bismuth trioxide alone.

Furthermore, additional burn time and ball lift testing of Example 25indicates the formulation maintains adequate flame retardancy andadequate resistance to ball-bond degradation comparable to formulationshaving antimony pentoxide alone.

The foregoing examples are intended to illustrate without limitation,the improved flame retardant epoxy molding compound, method andencapsulated device. It is understood that changes and variation can bemade therein without departing from the scope of the invention asdefined in the following claims.

What is claimed is:
 1. A semiconductor device encapsulated by a methodcomprising the using of a thermosetting epoxy molding compound in aliquid state in a mold surrounding a semiconductor device, said epoxymolding compound comprising:(a) about 5-25 percent by weight of compoundof an epoxy; (b) about 4-20 percent by weight of compound of aphenol-derived or a substituted phenol derived resin hardener; (c) aneffective amount of a catalyst for the reaction between said epoxy resinand said hardener in an amount of from about 0.1 to 10% by weight of thecombined weight of epoxy and hardener; (d) an effective amount of a moldrelease agent for the release of the cured molding compound from a moldin an amount of between about 0.01 and about 2 percent by weight ofcompound; (e) between about 50 and 85 percent by weight of compound of afiller; and (f) a flame retardant system of:(1) from about 0.4% to 0.8%antimony pentoxide by weight of molding compound; (2) from about0.01-1.0 percent sodium by weight of antimony pentoxide compound; (3) areactive organic compound containing at least about 1.0% of bromine byweight of molding compound which may include one or more of the othercomponents; and (4) from about 1.60 to about 4.0% bismuth trioxide byweight of molding compound.
 2. A semiconductor device according to claim1, wherein said hardener is a phenolic novolac.
 3. A semiconductordevice according to claim 1, wherein said epoxy molding compoundcomprises at least about 50 weight percent of an inorganic filler.
 4. Asemiconductor device according to claim 1, wherein said reactivebromine-containing organic compound is a polyglycidylether ofbromophenol-formaldehyde novolac.
 5. A semiconductor device according toclaim 1, wherein said reactive organic compound contains about 1.0 to1.8 percent of bromine by weight of the molding compound.
 6. Asemiconductor device according to claim 1, wherein said flame retardantsystem contains 0.03 to 0.06 percent of sodium by weight of antimonypentoxide.
 7. A semiconductor device according to claim 1, wherein saidflame retardant system contains about 1.60-3.20 percent of bismuthtrioxide by weight of the molding compound.